2,4-bis(methylsulfonyl)-benzeneazo-n-fluoroalkyl-n-hydroxyalkylaniline compounds



Patented Oct. 21, 1952 UNITED STATES PATENT OFFICE 22,4 BIS '(ME THYLSULFONYL) -:BENZENEAZO N- FLUO-ROAIZKYL- N -HY'DROXYALKYLAN ILINE COMPOUNDS Joseph B. Dickey, Rochester, N. Y,, assignor to Eastman Kodak Company, Rochester, N. 1 a corporation of New Jersey No Drawing. Application July 21, 1950, Serial No. 175,2 3

a cellulose. .alkyl carboxylic :acid :ester .having two 2 acetate propionate and cellulose acetate bu tyrate.

The 'new azo dye compounds of my invention are prepared by ,diazotizing a primary aromatic to fourcarbon atoms in the acid groups thereof. amine having the formula:

Isha-ve discovered that the new azo compounds having the general .formula: IL

CHaOzS and -.coupling .the :diazonium compound obtained with a compound having the vformula:

wherein R represents a QHzCI-IF2 group, a m CH2CF3 group, a Cl-I2CF2CH3 group, a .CH2C.H2CHF2 group or a .-C H2GH2GF3 group, R1 tenr entsa flhydroxye hyl roup. a fi-hydrOX-yDropyl group, a -hydroxypropyl'group or a .s -dihydroxypropy-l group, X represents a hydrogen atom, a chlorine atom, a bromine atom, v t a methyl group or an ethyl group, Y represents a R,R1, X, Y and Z in "the foregoing formulas have hydrogen atom, Z represents a hydrogen atom, a the meaning previously assigned to them. chlorine atom or a bromine atom and wherein Y The aromatic amine compounds having the also represents a methoxy group when X is a formula II that are used in the preparation of chlorine atom or a bromine atom are valuable the azo compounds rof any invention are: 2,4-bisdyes for coloring textile materials made of or (methylsulfonyl) aniline, 6 -br0mo 2,4 -bis containing a cellulose alk-yl carboxylic acid ester (methylsulfonyl) -aniline and G-chloro-EA-bishaving two to four carbon atoms in the acid to '(methylsulfonyDvaniline. groups thereof. These dye compounds when ap- Typical of the coupling compounds having the plied to the aforesaid materials give dyeings formula III that are used in the preparation of which have excellent light and gas iastness the azo compounds of my invention are: N-2,2- properties, They are particularly of use .for the difluoroethyl N c hydroxyethylaniline, coloration of cellulose acetate textile materials. N 2,2 difiuoro n -p ropy1 N c hydroxy- 'lhose compounds wherein Z is a hydrogen atom 'et-hylaniline, N "3,3 difiuoro -n propyl yield, dyfi'ings having yellowish-orange to red N c -hydroxyethylaniline, N 2,2,2 -trif1uoroshades whereas those compounds wherein "Z is a ethyl N B hydroxye'thy'laniline, "N 3,3,3 chlorine or bromine atom yield dyeings having trifiuoropropy'l N B hydroxyethylaniline, brownish-orange to brownish-red shades. 40 N 2,2 difluoroethyl N 8 hydroxypropyl- It is an object of my invention .to provide new aniline, N 2,2 difluoroethyl N 'y hydroxyazo dye compounds. Another object is to provide propylan'iline, N "2,2 difiuoroethyl N 5, a satisfactory process for the preparation of the dihydroxypropylaniline, N 222 difluoro n new azo dye compounds of the invention. A furpropyl N c hydroxypropylaniline, N 2,2 ther object is to provide. dyed cellulose alkyl difiuoroethyl N 19 -"hydroxyethyl m toluicarboxylic acid ester textile materials which dine, N 2,2 difiuoroethyl N ,8 hydroxypossess very good fastness to light and gas. A ethyl m -.ethylaniline. N -'2,2 difluoroethyl particular object is to provide new azo com- N '1 hydroxyethyl m -.chloraniline, N 2,2 pounds which are especially of value for the diiiuoroethyl -N -.B hydroxyethyl m bromodyeing of cellulose acetate textile materials. aniline, IN 2,2 difiuoroethyl -'N -13 hydroxy- By cellulose alkyl carboxylic acid esters having propyl .m toluidine, N 2,2 difluoroethyl two to four carbon atoms in the acid groups N .13 'hydroxypropyl m chloroaniline, thereon .1 mean to include, .fo x mp b N .2 l oroethyl N B y ox propv hydro y d nd unhyd l ed cellulose acetate m bromoaniline, 2,2,2 fiuoroe m N um jonate, cellulose butyrate, cellulose 13 hydroxypropylaniline, N 2,2,2 trifluoroethyl N 'y hydroxypropylaniline, N 2,2,2 triiiuoroethyl N ,B,'y dihydroxypropylaniline, N 2,2,2 trifiuoroethyl N 9 hydroxyethyl m toluidine, N 2,2,2 trifluoroethyl N {3 hydroxyethyl m chloroaniline, N 2,2,2 trifluoroethyl N B hydroxyethyl m bromoaniline, N 2,2,2 trifluoroethyl N B hydroxypropyl m toluidine, N 2,2,2 trifluoroethyl N p hydroxypropyl m chloroaniline, N 2,2-difluoroethyl N 5 hydroxyethyl 2 methoxy 5 chloroaniline, N 2,2 difluoroethyl N 8 hydroxyethyl -.2 methoxy 5 bromoaniline, N 2,2,2 trifluoroethyl N f3 hydroxyethyl 2 methoxy 5 chloroaniline, N 2,2 difluoro n propyl N 5 hydroxyethyl 2 methoxy 5 chloroaniline, N 3,3 difiuoropropyl N ,8 hydroxyethyl 2 methoxy 5 chloroaniline, N 3,3,3 -'trifiuoropropyl N ,8 hydroxyethyl 2 methoxy 5 chloroaniline, N 2,2 difluoroethyl N 13 hydroxypropyl 2 methoxy 5 chloroaniline, N 2,2 difiuoroethyl N 'y hydroxypropyl 2 methoxy 5 bromoaniline, N 2,2 difluoroethyl N o dihydroxypropyl 2 methoxy 5 chloroaniline, N 2,2,2 trifiuoroethyl N [3, dihydroxypropyl 2 methoxy 5 bromoaniline, N 2,2 difiuoro n propyl N 16,7 dih'ydroxypropyl 2 methoxy 5 chloroaniline and N 2,2 difluoro ethyl N 'y hydroxypropyl 2 methoxy 5 chloroaniline.

The following examples illustrate the azo compounds of my invention and their manner of preparation. Parts are expressed as parts by weight.

EXAMPLE 1 A. Nitrosyl siil furzc acid B. Diazotization 24.9 parts of 2,4-bis (methylsulfonyl) -aniline are added slowly, with stirring, to the nitrosyl sulfuric acid prepared as described above, while keeping the temperature below 20 C. When all the 2,4-bis(methylsulfonyl) -aniline has been added, 100 parts of acetic acid are added dropwise, with stirring, keeping the temperature between 15-20 C., and stirring is continued until all the 2,4-bis(methylsulfonyl)aniline has dissolved and diazotization is complete. The diazonium solution thus formed is then poured onto 500 parts of crushed ice, and enough urea is added to destroy the excess nitrous acid. The diazonium solution should be clear and free of suspended undiazotized amine.

C. Coupling A sulfuric acid solution is prepared by adding 10 parts of sulfuric acid (sp. gr. 1.84) to 20 parts of water. The sulfuric acid solution thus formed is cooled to 5 C. and 20.1 parts of N-2,2-difluoroethyl-N-p-hydroxyethylaniline are added with cooling. When solution is complete, 200 parts of ice and 200 parts of cold water are added. The diazonium solution prepared as described in B is then added slowly, with stirring, after which just sufiicient sodium carbonate to neutralize the CHZCHQOH OzCHa and melting at 200-201 C. are obtained. It colors cellulose acetate textile materials orange shades. It should be here noted that equally good dyes have been obtained when coupling was carried out in acetic acid or dilute hydrochloric acid.

EXAMPLE 2 By the use of 21.5 parts of N-2,2-difluoro-npropyl-N-;3-hydroxyethylaniline in place of N- 2,2 difiuoroethyl N ,6 hydroxyethylaniline in Example 1, the dye compound having the formula:

is obtained. It colors cellulose acetate textile materials orange shades.

EXAMPLE 3.

By the use of 21.9'parts of N-2,2,2-trifluoroethyl-N-B-hydroxyethylaniline in place of N2,2- difiuoroethyl N S hydroxyethylaniline in Example 1, the dye compound having the formula:

CHzGHzOH is obtained. It colors cellulose acetate textile materials yellowish-orange shades.

EXAMPLE 4 28.4 parts of 6-chloro2,4-bis (methylsulfonyD- aniline are diazotized in accordance with the procedure described in Example 1 for the diazotization of 2,4-bis(methy1sulfonyl) aniline and the diazonium compound obtained is coupled with 20.1 parts of N-2,2-difluoroethyl-N-/3-hydroethyl aniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 1. The dye compound obtained has the formula:

CHZCHFQ CHL CHQOH SOgCHa CHaOzS It colors cellulose acetate textile materials brownish-orange shades.

EXAIWPLE 5 Example 1, the dye compound having the formula:

zGZHzC'HF'l l (3520139011 802GB; Cl

is obtained. It colors cellulose acetate textile materials orange shades.

EXAMP nc 28.4 parts of .6-ch1oro -2, 4 -bis(methylsulfonyllaniline are diazotized and the diazonium .com-

pound obtained is coupled with 21.9 parts of N- 2,2,2-trifiuoroethyl -N '5 hydroxyethylaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example ,1. The dye compound obtained colors cellulose acetate textile materials brownish-orange shades.

EXAMPLE 7 28.4 parts of 6-chloro2,i-bistmethylsulfonyll-- aniline are diazotized and the .diazonium compound obtained is coupled with 21.5 parts of N 3,3 difluoropropyl-N-p-hydroxyethylaniline. Coupling and recovery or the dye compound formed is carried out in accordance with the procedure described in Example 1. Thedye compound obtained colors cellulose acetate textile materials brownish-orange shades.

32.9 parts of 6-bromo-2A-bis (methylsulfonyll 7 aniline are diazotized in accordance with the procedure described in Example 1 for the diazotization of 2,4-bis(methylsulfonyl)-aniline and the .diazonium compound obtained is coupled droxyethyla-niline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials brownish-orange shades.

EXAMPLE 9 By the use of 23.3 parts of N-3,3,3-trifluoropropyl-N-c-hydroxyethylaniline in place of N-2,2-

difluoroethyl-N-,3 ehydroxyethylaniline in Ex-- ample 1, a dye compound is obtained which colors cellulose acetate textile materials orange shades.

EXAMPLE "10 By the use oi 215 parts of N2,2-difiuoroethyl Nee-hydroxypropylaniline in place of N-2,2, di-

fiuoroethyl-N-B-hydroxyethylaniline in Example 1, a dye compound is obtained which colors cellulose acetate textile materials orange shades.

EXAMPLE 11 By the use of 21.5 parts of ZN-2,2 -difli-1oroethyl- N-v-hydroxypropylanili-ne in place of N-2,2-di

fluoroethyl-N-]3 hydroxyethylaniline in Example 1, a dye compound is obtained which colors cellulose acetate textile materials orange shades.

EXAMPLE 12 By the use oi.2.3.1 parts.of N-1'2,2-difiuoroethyl- N-B v-dihydroxynropylaniline in place of Ii-52,2 difiuoroethyl N-s-hydroxyethylaniline in .Example 1, a dye compound is .obtainedwhich colors cellulose acetate textile materials orange shades.

By the use of 21.5 parts of N-zffiifluoroethfl- N-e hydroxyethyl-m-toluidine in place of N-2;2- difiuoroethyl N-fi-hydroxyethyl'anlline in EX- ample 1, a dye compound is obtained which colors cellulose acetate textile materials orange shades.

EXAMPLE M 28.4 parts of fi-chloro-ZA-bis(methylsulfonyl) 7 aniline are diazotized and the diazonium compound obtained as coupled with 26.1 parts" of N 2,2,2 trifiuoroethyl -'N-fl.hydroxypropyl-methylaniline. Coupling and recovery of the dye compound formed is carried out. .in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials brownish-orange shades.

EXAMPLE 15.

By the use of 28 parts of N-2,2-difiuoroethyl- .N'B-hydroxyethyl-m-bromoaniline in place. of .N-ZB-difiuoroethyL-N-B hydroxyethylaniline.in Example .1, .a .dye compound is obtained which colors cellulose acetate textile materials orange shades.

EXAMPLE 1:6

By the use of 263 arts of N- 3,3,'3-trifluoropropy'l-N- 8,7-dihydroxypropylaniline in-plaoe of 'N- 2,2-difluoroethy1-N-fi-hydroxyethylaniline in Example 1, a dye compound is obtained which colors cellulose acetate textile materials orange shades.

EXAMPLE .1? v

32.9 parts of fi-bromo-ZA-Zbis(methylsulfonyli)-- aniline are diazotized and the diazonium com pound obtained is coupled with 26.5 parts o'tN- 2,2-difluoroethyl-N-;8-hy.droxyethyl-2 methoxy- 5-chloraniline. Coupling and recovery of the dye compound formed is carried out .in accordance with the procedure described in Example 1. The

dye compound obtained colors cellulose acetate textile materials brownish-orange shades,

EXAMPLE is v By the use of 32.8 parts of N-2;2,2-trifluoro- 'ethyl -N-c-hydrox'yethyl-Z-methoxy-d-bromoaniline in place of N -2,2-difluoroethyl-N -p-hydroxyethylaniline in Example 1, .a dye compound is obtained which colors cellulose acetate textile materials orange shades.

EXAMPLE 19 28.4 parts of 6-chloro-'2,4bis (methylsulfonyl) aniline are diazotized and the diazoniurn compound obtained is coupled with 29.3 partsoi N- 3,3-difiuoropropyl-N-78 hydroxypropyl 2- methoxy.5 -.chloroaniline. Coupling and recovery of the dye compound .formed is carried out in accordance with the procedure describedlin Example 1. The dye compound obtained colors ce1- lulose acetate textile materials red shades.

EXAMPLE 20 By the use of 32.4 parts of NuZfi-(ilfillOlfO'Ifi propyl-N-fi-hydroxyethyle2 amethoxy 5 -'.br.omoaniline in place of N-2,2-difluoroethyl-N-phydroxyethylaniline in Example 1, a dye compound is obtained which .colors cellulose acetate textile materials orange shades.

EXAMPLE 21 By :the use of 126.? parts or rr-.2,-2,2-trifi uemethyl-.N-v hydroxypropyl rm chloroaniline in 7 place of N-2,2-difluoroethyl-N-p-hydroxyethylaniline in Example 1, a dye compound is obtained which colors cellulose acetate textile materials yellowish-orange shades.

EXAMPLE 22 By the use of 22.9 parts of N-2,2-difluoroethyl- N-fl-hydroxyethyl-m-ethylaniline in place of N- 2,2-difiuoroethyl-Nfi-hydroxyethylaniline in Example l, a dye compound is obtained which colors cellulose acetate textile materials orange shades.

EXAMPLE 23 7 By the use of 25.3 parts of N-2,2,2-trifiuoroethyl-N-fi-hydroxyethyl-m-chloroaniline in place of N 2,2 difluoroethyl-N-B-hydroxyethaniline in Example 1, a dye compound is obtained which colors cellulose acetate textile materials yellowish-orange shades.

' EXAMPLE 24 32.9 parts of 6-bromo-2,4-bis(methylsulfonyl) aniline are diazotized and the diazonium compound obtained is coupled with 29.4 parts of N 2,2 -difluoroethylN-' -hydroxypropyl-m-bromoaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials brownish-orange shades.

EXAMPLE 25 By the use of 22.9 parts of N3,3-difluoropropyl- N-fl-hydroxyethyl-mtoluidine in place of N-2,2- difluoroethyl-N-p-hydroxyethylaniline in Example 1, a dye compound is obtained which colors,

cellulose acetate textile materials red shades.

EXAIVLPLE- 26 28.4 parts of 6-chloro-2,4-bis(methylsulfonyl) aniline are diazotized and the diazonium compound obtained is coupled with 23.3 parts of N- 2,2,2 trifluoroethyl N-fi-hydroxyethyl-m-toluidine. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials brownish-orange shades.

EXAMPLE 27 By the use of 26.? parts of N-3,3,3trifluoropropyl-N-p-hydroxyethyl-m-chlcroaniline in place of N-2,2-difluoroethyl-N-fi-hydroxyethylaniline in Example 1, a dye compound is obtained which colors cellulose acetate textile materials orange shades.

EXAMPLE 28 28.4 parts of 6-chloro-2,4-bis(methylsulfonyl) aniline are diazotized and the diazonium compound obtained is coupled with 24.5 parts of N-3,3-difluoropropyl-N-fi-' -dihydroxypropylaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials brownish-red shades.

EXAMPLE 29 32.9 parts of 6-bromo-2,=l-bis(methylsulfonyl) aniline are diazotized and the diazonium compound obtained is coupled with 243 parts of N 2,2-difluoro-n-propylN-fi-hydroxypropyl-mtoluidine. Coupling and recovery of the dye compound formed is carried out in accordance with 8 the procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials brownish-red shades.

EXAMPLE 30 28.4 parts of 6-chloro-2,4-bis(methylsulfonyl) aniline are diazotized and the diazonium compound obtained is coupled with 23.5 parts of N-2,2-difluoroethyl-N-;8-hydroxyethyl-m-chloroaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials brownish-orange shades.

EXAMPLE 3 1 32.9 parts of 6-bromo-2 l-bis(methylsulfonyl) aniline are diazotized and the diazonium compound obtained is coupled with 28.1 parts of N- 2,2-difluoroethylN-;9-hydroxyethyl-m-bromoaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials brownish-orange shades.

EXAMPLE 32 28.4 parts of 6-chloro-2,4-bis(methylsulfonyl)- aniline are diazotized and the diazonium compound obtained is coupled with 22.9 parts of N- 2,2-difiuoro-npropyl-N-' -hydroxypropylaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials brownish-red shades.

EXAMPLE 33 28.4 parts of 6-chloro-2A-bis(methylsulfonyl) aniline are diazotized and the diazonium compound obtained is coupled with 25.1 parts of N- 3,3 difluoropropyl N p- -dihydroxypropyl-mtoluidine. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials brownish-red shades.

EXAlVEPLE 34 28.4 parts of 6-chloro-2,4-bis(methylsulfonyl) aniline are diazotized and the diazonium compound obtained is coupled with 23.3 parts of N- 333 trifluoropropyl N 3-hydroxyethylaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials brownish-orange shades.

EXAMPLE 35 pressure.

Diazo Component Coupling Component Color 2,4-bis(methylsulfenyD-anilin.. N 2,2=diflucro-n propyl-N- orange.

B-hydroxyethylaniline, Do N 2,2-difluro-n propyl N- Do.

fl-hydroxyethyl-ni-ohloreaniline. v V De N-2,2,2-trifluoroethyl-N-fi- Do.

hydrox'ythylaniline. De N-2 ,2-,2-trifluoroethyl-Nf-fi,y- Do.

dihydroxypropylaniline. Do -N- 3,3-difluoropropyl-N fl- Do.

hydroiiyethylaniline. D0 N -3,B-diiluoropmpYhN-flred.

hydreXyethyl-m-ethylani e-J 6-ohloro-2,4-bis (methylsnlfonyl) N -2,2-di floor 0 a th yl N -18- brownish-erange.- v aniline. hydroxyethylaniline.

D0 N-2,2-diflueroethyl-N fl Do.

hydrexyethyl-2-methoxy- -ohloroaniline. I Do N-.3,3,3-triiluoropropyl-N;B- brownish-red.

hy'dioxyethyl-2-metl1oxy h weni 1e;- i 6-brom0-2,4-bis(methylsulfonyl)- N-3,3-diiluoropropyl N flbrownish-orange.

aniline. hydrox-yethylaniline. I

Do j. N'3.3-diilnopepropyLN-d brownish-red.

hydroxyetliylmcbloroaniline. Do N-2'Z-difillQIjOetHyhN-fim Do.

dihydroxypropylaniline.

Dye compounds corresponding to these described hereinbefore but which contain at least one OSO3H group orthis-greup in its salt form have also been prepared. These dye compounds containing a sulfate group are prepared either by introducing a sulfate group into the dye compounds previously described or by introducing a sulfate groupin'te the coupling components of the present' invention and coupling the compounds thus obtained with the diazonium' compounds used in the preparation of the new azo compounds of the invention. These new dye compounds are suitablefor dyeing the textile materials mentioned hereinbefore as well as silk, weed and nylon textile materials. .Because of the increased water solubility of these new dye compounds, they are particularly adapted for dyeing cones of yarn .andfabrics-o'f close weave and of heavy construction.

The following examples illustrate the manner in which these new sulfate dye compounds are 500 cc. of carbon tetrachloride and the resulting solution is cooled to 10 C. Then 12.? grams of freshly distilled chlorosulfonic acid-are added dropwise with stirring overa period of 3 hours. After the addition of the chlorosulfonic acid, the reaction mixture isslowly' warmed to C. and maintained at this temperature for several hours. Heating is thendiscontinued and; the carbon tetrachloride is distilled offunder reduced 300 cc. of ice end water-are then added to the reaction mixture and the dye is recovered by evaporation. If'a salt 'formof the dye is desired, theevaporation step' is' omitte'd. Instead, following the-addition of the 300 00. of ice and water, the reaction mixtureis neutralized with sodium hydroxide- (other suitable organic or inorganic leases can loc used),-warined to;dis-

solve the dye, filt'eredto remove any insoluble SOiCHt' CHaO2 cellulose acetate; .wool;

It colors cellulose acetate, wool, nylon and silk textile materials orange shades.

EXAMPLE 3'? 47.5 grams of 2,4-bis('methylsulfonyl) benzeneazo' N 2,2 difiuoro-ri -propyl N l3 hydroxyethylani-line -(-dye'.of Example 2) are dissolved in 200 cc; of pyridine and the resulting sol-utionis cooled to5 C. Then 12.7 grams of chle'rosulfonioacid are added dropwisewith stirring over a periodof 3hou'rs. Stirring is continued' for an additional 2 hours following which the reaction mixture is-heated 11050 C. and maintained at this temperature for two hours. Following this the reaction mixture is cooled and the pvridineis removed under reduced pressure. 300 cc. of ice and Water are the'n added to the reaction mixture and the dye is recovered by evaporation. The dye compound obtained colors cellulose acetate textile materials orange shades. I 1

' EXAMPLE 33 49 .5 grams of;6-chloro-2, l-lois (methylsulfonyl) benzeneazo N 21,121. difluoroethyl N' phydroxyethylanilinegdye of Example' l) are mixed with 50. cc. of sulfuric acidlsp. gr. 1 .84) and'the reaction: mixture-resulting isiwanheo to 50. C. for

3 hours and then cooled to 0 C. 200 cc. of ice and Water are added and thereaction nnxture 1 is made neutral toCongo'Red paper with sodium 24.9 grams of 2,4-bis(methylsu1fenyl)-aniline are unz ti edi a q edeneew th th pro d r described in Examplel-and thejdiaaonium' coinpound obtained is coupled with 32:1 grams of the sodium salt of N- 2,2,2-trifiuoroethyl-N-B- sulfatoethylaniline. Coupling and recovery of the dye compound formed is/carried out in accorclance with the procedure described in Example 1. The dye compound obtained colors silkzand; nylon yellowishorange shades. a I

.From the-i1.foregoingexamples; the manner of introducing-a sulfa-to= groupz'into any-.- of, the are compounds of my invention iseb'elieyed tobe clear, especially since the manner of introducing a sulfato group is known to those skilled in the art. Any other suitable way of introducing the sulfato group into the dye molecule can be employed. The sulfato group can be present in its free acid form or in the form of an inorganic or organic base salt such as, for example, the Na, K, NH4, Mg, Ca, Li, methylamine, dimethylamine, trimethylamine, pyridine, aniline, guanidine, semicarbazide, biguanidine, phenyl guanidine, cyclohexylamine, dicyclohexylamine, tetrahydrofurfurylamine or alkanolamine salt form.

In order that the preparation of the azo compounds of my invention may be clearly understood, the preparation of certain intermediates used in their manufacture is described hereinafter.

Example A.-6-chloro-2,4-bis(methylsulfonyl)- aniline 24.9 grams of 2,4-bis(methylsulfonyl) aniline suspended in 100 cc. of concentrated HCl and 50 cc. of glacial acetic acid were placed in a 500 cc., B-necked fiask fitted with a stirrer and cooled in an ice bath and than 0.5 gram of FeCls were added.

Chlorine was bubbled slowly into the reaction mixture, while stirring, and while keeping the temperature at 20 C.-25 C. for 4-5 hours. The reaction mixture was then drowned in an excess of cold Water to precipitate the 6-chloro-2,4-

is(methylsulfonyl)-aniline formed by the reaction and which was recovered by filtration, washed neutral and dried. About 26.2 grams of a straw-colored crystalline product was obtained.

Example B.-6-bromo-2,4-bis(methylsulf-onyl) aniline 24.9 grams of 2,4-bis(methylsulfonyl)-aniline suspended in 100 cc. of concentrated HCl and 30 cc. of glacial acetic acid were placed in a 500 cc., 3-necked flask fitted with a stirrer and cooled in an ice bath. 16 grams of bromine dissolved in 30 cc. of glacial acetic acid were gradually added, with stirring, over a period of 4 hours while maintaining the temperature at 20-25 C. The reaction mixture was then poured into an excess of cold water to precipitate the G-bromo- 2,4-bis(methy1sulfonyl)-aniline formed by the reaction and which was recovered by filtration, washed with cold water and dried. About 29.5 grams of a yellow crystalline product was obtained.

2,4-bis(methylsulfonyl)-aniline is a known compound. It is a substantially white crystalline solid melting at about 199-202 0.

Compounds having the formula:

omorcon N l R X are prepared by reacting ethylene oxide with a compound having the formula:

numbered IV are prepared.

12 Example C'.N-2,2-difluo1'oethyl-N-p-hydromyethylaniline 15.7 grams of N-2,2-difiuoroethylaniline, 5.2 grams of ethylene oxide and 15 cc. of ethyl alcohol are sealed in a glass tube and heated at 200 C.-205 C. for 18-20 hours with shaking in an autoclave. Upon distillation of the reaction mixture under reduced pressure through a 10 indented column, 18 grams of N -2,2-difluoroethyl-N-fi-hydroxyethylaniline boiling at 123 C.-125 C./3 mm. are obtained. About 1.5 grams of N-2,2-difluoroethylaniline are also recovered.

Example D.N-2,2-difluoro-n-propyl-N-fi-hydroxyethylaniline 7.9 grams of N-2,2-difiuoro-n-propylaniline, 1.9 grams of ethylene oxide and 10 cc. of ethyl alcohol are heated with shaking in a sealed tube for 8 hours at 185 C. The contents of the tube are cooled, removed from the tube and distilled under reduced pressure. About 3 grams of N- 2,2 difluoro n propyl N fl hydroxyethylaniline boiling at C.- C./11 mm. are obtained.

droxyethyl-m-chl0*roaniline 7.6 grams of N-2,2-difluoro-n-propyl-m-chloroaniline, 1.9 grams of ethylene oxide and 5 cc. of ethyl alcohol are heated with shaking in a sealed tube for 15 hours at 200 C. Then the contents of the tube are cooled, removed from the tube and distilled under reduced pressure. 3 grams of N-2,2-difluoro-n-pr-opyl-N-fi-hydroxyethyl-m-chloroaniline boiling at C.-1'70 C./6 mm. are obtained.

Example F.N 2,2,2 triflum'oethyl N fl hydroxyethylaniline 13.5 grams of N-2,2,2-trifiuoroethylaniline, and 4.84 grams of ethylene oxide dissolved in 10 cc. of ethyl alcohol are sealed in a glass tube and heated at 210 C.-220 C. for 20 hours, with shaking, in an autoclave. Upon cooling, the contents of the tube are removed. After removal of the alcohol by distillation at atmospheric pressure the reaction mixture is distilled under a reduced pressure of 1-2 mm. 16 grams of N-2,2,2-trifiuoroethyl-N-,8-hydroxyethylani1ine boiling at 102 C.-103 C./1.5 mm. are obtained.

Example G.N-3,3,3-trifluoropropyl-N-flhydromyethylaniline 28.4 grams of N-3,3,3-trifiuoropropylaniline and 8 grams of ethylene oxide dissolved in 30 cc. of ice-cold ethyl alcohol are placed in an icecold glass tube. The tube is sealed and fastened into a shaking autoclave and heated at C. for 24 hours with shaking. Upon cooling the autoclave and opening the tube, the reaction product is fractionated directly, first under atmospheric pressure to remove the ethyl alcohol and then under a reduced pressure of about 2 mm. An 84% yield of N-3,3,3-trifluoropropyl-N-;8-hydroxyethylaniline boiling at 119 C.-120 C./2 mm. N 1.5018 is obtained. Some unreacted N-3,3,3- trifiuoropropylaniline is also recovered and distills over prior to the desired reaction product.

Example H .N -2,2,2-trifluoroethyl-N -,8- hydromyethyl-m-chloroaniline grams of N-2,2,2-trifiuoroethyl-m-chloroamline and 5.2 grams of ethylene oxide dissolved sample Example I .-'-N -2 ,2,2.-tr ifluoroeth11 Z-N 13- hydrozcyethyZ-m-chloroaniline 20.9 grams of N-2,2,2-trifluoroethyl-m-chloro aniline and 5.2 grams of ethylene oxide dissolved in 10 cc. of ice-cold ethyl alcohol are placed in an ice-cold glass tube. The tube is sealed and fastened ina shaking autoclave which is heated to 185' C.-195 C. and maintained at this temperature for 16 to 18 hours. Upon cooling, the reaction mixture is removed from the tube and fractionated directly, first under atmospheric pressure to remove the ethyl alcohol and then under a reduced pressure of about 1 mm. l 8 grams of N-2,2,2-trifluoroethyl-N-;3hydroxyethy1-m-chloroaniline boiling at 134 C.-137 C. are obtained.

In a manner similar to that described in Examples C, D, E, F, G, H and I, N-2,2,2-trifluoro ethyl-N-p-hydroxyethyl-m-toluidine, B. P. 103 C.-104 C./2 mm.; N-2,2,2-trifluoroethy1-N-/3- hydroxyethyl-m-ethylaniline, B. P. 114 C.'-1.1,'7

ethyl-m-bromoaniline, B. P. 153 -157 C./2 mm.; N--3,3,3-trifluoropropyl-N-;8-hyd-roxyethylm ohloroaniline, B. P. 145 0/2 mm.; N-2,2-difiuoroethyl N p-hydroxyethyL-m chloroaniline, B. P. 180 0/14. mm.; N-2-,2-difluoroethyl-N- 3- hydroxyethyl-m-toluidine, B, P, 120 0/2 mm.; N 2,2 difiuoron-propyl-N-/3hydroxyethyl-methylaniline, B. P. 130 C.132 C./1 mm.; N-3,3- difluoropropyl-N-/3 hydroxyethy1ani1ine,B. P. 135 C.-l36 C./ 2 mm.; N 3,3-difluoropropyl-N-p-hydroxyethyl-m-toluidine, B. P. 130 0/1 mm.; N- 33 difiuoropropyl N-B-hydroxyethylm-ethylaniline, B. P. 131 C.-132 C./1 mm.; N-2,2-difluoro n-propyl-N-B-hydroxyethyl-m-ethylaniline, B. P. 131 C.-132 C./1 mm.; N-2,2-difiuoroethyl-N-flhydroxyethyl 2 methoxy-S-chloroani1ine, N- 2,2,2 trifluoroethyl N B-hydrOXyethyI-Z-methoXy-5-bromoaniline, etc. are prepared.

Compounds having the formula:

CHzCHzCHaOH wherein R, X and Y have the meaning previously assigned to them are prepared by reacting trimethylene ohlorohydrin (C1CH2CH2CH2OH) or trimethylene bromohydrin (BrCHzCI-IzCHzOI-I) with a compound having the formula V.

The following examples are illustrative of the manner in which the compounds having the formula numbered VI are prepared.

Example J .--N -2,2,2 -trifluoroethyl-N-'y-hydroxypropylaniline 525 grams of N-2,2,2- trifluoroethylaniline and "14 heated 'togetlier on' a steam bath for 10- hours. The reactionmixture is cooled and 10% aqua ous' NaOH" is added thereto until i'tis alkaline. The reaction mixture-is then treated berrzene and the-benzene portion is removed, washed with water and distilled under reduced pressure: N 2,2,2 trifiuoroethyl Nw hydroxypropylani lit-labelling at 1 22 C.-I24 C./2 Obtained.

561 grams of -N-2,2,2-trifiuoroethyl-mr-tolui dine, 46A grams of trimethylenebromohydrin and 30.5 grams of NaHCOa are heated at Ctfor. 6 hours with stirring. Upon coolin benzene is added to the reaction mixture and the reaction mixture is filtered. The benzene is removedfrom the filtrate, for-"example, by distillation over a water bath, and the portion remaining is disti1led under reduced pressure to Obtain N-2,"2,2-trifluoroethyl-N-" -hydroxypropyl-m-toluidine' boiling at 126 C.1'2'8C'./2"mm.

Example L.-N-2,2-difluoroethgjlsN-y hydromw propyZ-m-toluidine 51.3 grams of 'N- 2,2edifluoroethyl-m-toluidine are reacted with 30 grams of trimethylene chlorohyd'rinin accordance with the procedure 'described in Example J. N-2,2-difluoroethyl-N-'yhydroxypropyl-m-toluidine boiling of; 134 C:- 138 C./2 mm. is obtained.

Following'the" procedure described in Examples J, K and L, N-2,2,2-trifiuoroethyl-N- .-hyd'roxypropyl-m'-ch1oroaniline,. B. P. 154' C.- 1'57; C./2.5 mm.; N-'2;2,2-trifluoroethyl-N -hydroxypropyl-mbromo'aniline, B. P. C.- C./2.5 mm.; N-3,3,3trif1uOrOp1'0py1-N -7- hydro cypropylaniline', B. P. 131 C.-135 C./2' mm.; N-3,3,35triflu'oropropyl-N'- *y hydroXypropyl -ml R X VII wherein'R, X a'ndY. have'the meaning previously assignedto them are prepared by reactingglycerol chlorohydrin with a compound. having the Formula. V. V The following examples are illustrative of the --manner in which the compounds havingtheformula-numbered VII are prepared.

hydrowypropylam'line H 17- grams or- N2,2=d1rruom=n ropyiamnn '15 grams of NaHCOa, 100 cc. of amyl alcohol and 12 grams of glyceryl chlorohydrin are heated together under refluxing conditions for 6-10 hours. Then 2 grams of charcoal are added and the reaction mixture is stirred and filtered to remove the charcoal, salt and any other insoluble material. The amyl alcohol is removed by distillation under reduced pressure and then the reaction mixture is steam-distilled under reduced pressure to remove any unchanged N-2,2-difluoro-n-propylaniline. Following this the reaction mixture is extracted with benzene and the benzene extract is distilled to dryness under reduced pressure. N- 2,2-difiuoro-n-propyl N B/v dihydroxypropylaniline is obtained. It is a straw-colored, viscous compound.

Example N.N-2,2,2-trifluoroethyl-N-p -dihydromypropylamlz'ne This compound is obtained by reacting 17.5 grams of N-2,2,2-trifiuoroethylaniline, 10 grams of NaI-ICOa, 100 cc. of amyl alcohol and 12 grams of glyceryl chlorohydrin together in accordance with the procedure described in Example M.

Example O.N-3,3,3-trifluoropropyl-N-e'y-dihy.-

, droxypropylaniline 18.9 grams of N-3,3,3-trifluoropropylaniline and 9.2 grams of NaHCO3 are stirred and heated together at 145 C. on an oil bath while 12.2 grams of glyceryl chlorohydrin are slowly added. After the addition, heating and stirring at 145 C. are continued for 6 hours. An equal volume of water is then added to the reaction mixture and the Ewample P.N-3,3,3-trifluoropropyl-Nl ry-dih.y-

droxypropyl-m-toluidine 19.9 grams of N-3,3,3-trifiuoropropyl-m-toluidine, 9.2 grams of NaI-ICO3 and 12.2 grams of glyceryl chlorohydrin are heated together under refluxing conditions for '7 hours. Then 2 grams of charcoal are added and the reaction mixture is stirred awhile and then filtered to remove the charcoal, salt and any other insoluble material. The crude reaction product thus obtained is distilled in a molecular still under a reduced pressure of 13 microns at 95 C.lOO C. N-3,3,3-trifiuoropropyl-N-fi,- -dihydroxypropyl-m toluidine is obtained.

Following the procedure described in Examples M, N, O and P, N-2,2,2-trifluoroethyl-N-5,' dihydroxypropyl m chloroaniline, N-2,2,2-trifiuoroethyl-N B -dihydroxypropyl-m-toluidine, N -3,3,3 -trifiuoropropyl N-Bxy dihydroxypropylm-chloroaniline, N-2,2-difiuoroethyl-N-/3,'ydihydroxypropyl-m-toluidine, N-2,2-difluoro-n-propyl-N-p -dihydroxypropyl-m-bromoaniline, N- 2,2-difluoro-n-propyl-N- B,'y-dihydroxypropyl-mtoluidine, N-3,3-difluoropropyl-N-;8; -dihydroxypropylaniline, N-2,2-difiuoroethyl N ,9,vdihydroxypropylaniline, N-3,3-difiuoropropyl-N-dydihydroxypropyl-m-chloroaniline, N-2,2-difluoroethyl N ,fm-dihydroxypropyl-m-ethylaniline, N-2,2-difiuoroethyl N 1 7 dihydroxypropyl-2- methoxy-5-chloroaniline, etc. are prepared.

1 6 Compounds having the formula:

vrn Y CHzCHOHCH:

LN \R wherein R, X and Y have the meaning previously assigned to them are prepared by reacting propene oxide (propylene oxide) having the formula:

OCHzCHCH:

with a. compound having the formula V.

The following examples are illustrative of the manner in which the compounds having the formula numbered VIII are prepared.

Example Q. N-2,2-difluoroethyZ-N-p-hydromypropylamline 15.7 grams of N-2,2-difluoroethylaniline, 6.85 grams of propene oxide and 15 cc. of ethyl alcohol are sealed in a glass tube and heated at 200 C.205 C. for 18-20 hours, with shaking, in an autoclave. Upon distillation of the reaction mixture under reduced pressure about 18 grams of N-Z,2-difiuoroethyl-N-fi-hydroxypropylaniline boiling at 131 C.138 C./3 mm. are obtained.

Example R. N 2,2,2 trifiuoroethyl N B- hydromypropylaniline 13.5 grams of N-2,2,2-trifiuoroethylaniline, and 6.38 grams of propene oxide dissolved in 10 cc. of ethyl alcohol are sealed in a glass tube and heated at 210 C.220 C. for 20 hours, with shaking, in an autoclave. Upon cooling, the contents of the tube are removed and distilled at atmospheric pressure to remove the ethyl alcohol, after which the reaction mixture is distilled under a reduced pressure of, for example, 1-2 mm. About 16 grams of N-2,2,2-trifluoroethyl-N-5-hydroxypropylaniline boiling at about C.- 111 C./1.5 mm. are obtained.

Example S. N 3,3,3 trifluoropropyl N ehydroxypropyl-m-toluidine 30.5 grams of N-3,3,3-trifluoropropyl-m-toluidine and 10.5 grams of propene oxide dissolved in 100 cc. of ice-cold ethyl alcohol are placed in an ice-cold autoclave glass liner. The liner is then placed in an autoclave and heated at 185 c. for 24 hours with shaking. Upon cooling the autoclave, the reaction mixture is removed and fractionated directly, first under atmospheric pressure to remove the ethyl alcohol and then under a reduced pressure of about 2 mm. About an 80% yield of N-3,3,3-trifiuoropropyl-N-fl-hydroxypropyl-m-toluidine boiling at about 136 C.l37 C./2 mm. is obtained. Some unreacted N 3,3,3 trifiuoropropyl n1 toluidine which distills over prior to the desired reaction product is also recovered.

Following the procedure described in Examples Q, R and S, N-2,2-difluoro-n-propyl-N-B-hydroxypropylaniline, B. P. 163 C.l68 C./l1 mm.; N 2,2 difluoro n propyl n ,8 hydroxypropyl-m-chloroaniline, B. P. 1'73 C.178 C./6 mm.; N-2,2,2-trifluoroethyl-N-p-hydroxypropylm-toluidine, B. P. 111 C.l12 C./2 mm.; N-2,2,2- trifiuoroethyl N b hydroxypropyl m ethylaniline, B. P. 122 C.125 C./l.5 mm.; N-2,2,2- trifiuoroethyl N ,3 hydroxyethyl m bromoaniline, B. P. 161-165 C./2 mm.; N-3,3,3-trifluoropropyl N fl hydroxypropyl m chloroaniline, B. P. 153 C./2 mm.; N-2,2-difluororespectively.

1ethyleN-B-hydroxypropyl-m-chloroaniline, B. P.

.hydroxypropyl-m-toluidine, B. P. 128 C./2 mm.;

N. 3,3 difiuoropropyl N 3 hydroxypropylaniline, B. P. 143-144 C./'2 mm.; N-3,3-difiuro propyl N 18 hydroxypropyl m toluidine,

vB. P. 138 C./1 mm.; N-2,2-difluoro-n-propyl- 140 C./1 mm.; N 2,2 difluoroethyl N [3 hydroxypropyl-2-methoxy-5-chloroaniline; etc. are prepared.

Compounds having the formula numbered V are preparedbyreacting a compound having'the formula:

IX Y

wherein .X, and Y have the, meaning previously assigned to, them, with 1,1-difluoro-2-bromoethane or 1,1-difluoro-2-chloroethane, 1,1,1-trifiuoro-Z-bromoethane or 1,1,1-trifiuoro-2-chloroethane,- 3,3*difluoro-n-propylbromide 2,2 difluoro n propylbromide (CI'I3CF2CH2BI) and 1,1,1-trifluoro-3-chlor.opropane (CFsCI-IzCHzCl) The following examples are illustrative of the manner in which the compounds having the formulanumbered V are prepared.

Ercample T.N-2,2-difluoroethylanilin 72.5. grams, of 1,1-difiuoro-2-bromoethane, 46.5 grams of aniline, 42 grams of sodium bicarbonate and 1 gram of sodium iodide are heated together with shaking in an autoclave for 15 hoursat 150 C. After cooling to room temperature, the reaction mixture is removed from the autoclave by washing with benzene (200 grams) and water and filtered to remove a small amount of insoluble material. The benzene layer is washed with water and then the benzene is removed by distillation. Upon distillation under reduced pressure through a 12" indented column, 66 grams of N-2,Z-difluoroethylaniline, boiling at 104 0-106 C./ 19 mm. are obtained.

Example U.N-2,2-difluoro-n-propylaniline 28 gramsof aniline, 4.3 grams of 2,2'-difluoron-propylbromide, 25 grams of sodium bicarbonate and 1 gram of sodium iodide are placed in an autoclave and heated 24 hours at 170 C. with shaking. The reaction mixture is then cooled, washed out of the autoclave with benzene and filtered. The benzene is then removed from the filtrate and the residue containing the desired reaction product is distilled under reduced pressure. A good yield of N-2,2-difluoro-n-propylaniline boiling at 103 C.-'7 C./ 12 mm. is obtained.

Example V.-N-3,3-clifiuoro-n-propylaniline By use of 43 grams of- 3,3-difiuoro-n-propylbromide in place of 2,2-difluoro-n-propylbromide in Example W, N-3,3-difluoro-n-propylaniline boiling at.125. C.-.-126. C../l6 mm. isobtained.

Example W.'N-'3,3,3-trifluoropropylaniline 46.5 grams of aniline and 33.3 grams of CEsGHzCHZCl are placed in a glass. tube. The

' tube is sealed, fastened in a shaking autoclave and heated up to 185 C. with shaking. Heating at 185 C. with shaking is continued for 24 hours and then the autoclave is cooled. On openin the tube, the reaction mixture is treated with an excess of 10% llaOI-I solution to decompose any aniline hydrochlorides present, and the oily layer is taken up in a small amount of benzene. The benzene layer is washed until neutral and dried over Drierite (anhydrous calcium sulfate) after which, it is fractionated under atmospheric pressure to remove the benzene and then under a reduced. pressure of about 15mm. Aniline is first recovered and then better thana 50% yield of N-3,3,3-trifluoropropylaniline boiling ail-101 C.- .103 C./1..5 mm-,.N -1.4847.

Example X.--N-3.,3,3 trifluoropropyl-m toluidine 53.5 grams of m-toluidine and 33.3 grams of CFaCI-l'zCI-IzCl are heated in a sealed tube in a shaking autoclave at 185 C. for 2% hours in accordance with the procedure described in Example W. A good yield of l l-3,3,3-trifluoropropylrn-toluidine boiling at 114: 0-116 (3/15 mm., N 1.4848 is obtained.

Example Y.-N-2,2,2-trifluoroethylaniline 40 grams of 1,1,1trifiuoro-2-chloroethane and 64.6 grams of aniline are placed in a glass tube cooled in an acetone Dry Ice bath. The tube is sealed, fastened in a shaking autoclave and heated at 250 0-255 C. for thirty hours. Uponcooling, the tube is opened and the contents poured into a mixture of 420 cc. of water and grams of hydrochloric acid (sprgr. 1.18). The dilute acid completely dissolves any unreactecl aniline while the 'less basic N-trifluoroethylaniline and byproduct diphenylamine are insoluble. The re action mixture is extracted with two 50-gram portions .ofbenzene. The two benzene extracts are combined, washed freeof acid and then distilled under a reduced pressure of about 15 mm. 24.1,grams of N-2,2,2-triflucroethylaniline boiling at 84 0-85 C./l5 mm., N 1.4820 are obtained.

Following the procedure described inExamples T, U, V, W, X and Y, N -2,2-difiuoroethyl-m-toluidine, B. P. 140 0-141 C./27 mm.; N-2,2-difluoroethyl-m-chloroaniline, B. P. 129 C.-133 C./1.6 mm.; i l-2,2-difluoro-n-propyl-m-toluidine, B. P. 1150-117 C./l.'2 mm.; Ill-2,2-difiuor0-n-propylmeethylaniline, BQP. 120 -C.-123 C./12 mm.; N- 2,Z-difluoro-n-propyl-m-chloroaniline, B. P. 11.5 (LE-120' C./'7 mm.; N-2,2-difluoro-n-propy1-mbromoaniline, B. P. 125 (3-128 C./7 mm.;.N-3,3- difiuoro-n-propyl-rntoluidine, B. P. 146 (LE-14,7 C./27 mm.; N.-3,3-difiuoro-n-propyl-m-chloro- Example Z.-P1'eparation of 1,1 -dz'fluoro =3- bromopropane 98* grams or 1,1,3-tribromopropane. were placed in a200 cc. round-bottomed flask fitted witha still-head and a well-cooled receiving flask. 107 grams of dry mercuric fluoride were then added and the reaction flask was gently heated with a free flame until reaction began. The reaction was then allowed to proceed briskly but not too vigorously (by cooling in a bath of ice water or heating, as required) until all the reaction product has distilled over at about 85 C.-100 C. The crude product was then steam-distilled, dried and fractionated. The main product was 1,1-difiuoro-3-bromopropane, boiling point 92 C.-94 C. Using this procedure yields of 3540% of pure 1,1-difluoro-3-bromopropane are obtained. A small amount of CHzFCHzCI-IzBr was present in the residue.

1,1,3-tribromopropane (CHBrzCHzCHzBr) likewise appears to be a new compound. It was prepared as described hereinafter.

Example AA.-Preparation of 1,1,3-tribromopropane 1000 grams of bromoform and 30 grams of benzoyl peroxide were placed in a 1100 cc. shaking autoclave and ethylene was passed into the autoclave until a pressure of 700 lbs. per sq. inch was reached. The reaction mixture was then heated at 85 C. for hours following which it was cooled, removed from the autoclave and fractionated under reduced pressure. About 600 grams of 1,1,3-tribromopropane boiling at 105 C. 107 C./30 mm. were obtained. Using the procedure just described or generally similarly procedures somewhat higher and somewhat lower yields were obtained. As high as 700 grams have been obtained. Also 100-150 grams of bromoform, -30 grams of a low boiling liquid and varying amounts of higher boiling compounds are recovered.

The azo dye compounds of my invention can be applied to the textile materials named hereinbefore in the form of an aqueous dispersion and are ordinarily so applied. To illustrate, the dye compound is finely ground with a dispersing agent such as sodium lignum sulfonate, Turkey red oil, soap, or an oleyl glyceryl sulfate and the resulting mixture is dispersed in water. The dye bath thus prepared is heated to a temperature approximating 45 C.-55 C. and the textile material to be dyed is immersed in the dyebath, following which the temperature is gradually raised to 80 C.90 C. and maintained at this temperature until dyeing is complete, usually one-half to two hours. From time to time throughout the dyeing operation, the

material is worked to promote even dyeing.

Upon completion of the dyeing operation, the textile material is removed from the dyebath, washed with an aqueous soap solution, rinsed well with water and dried.

The procedure just described is applicable whether the dye compound contains a sulfato group or not. The dye compounds of the invention not containing a sulfato group are practically water-insoluble. Where a sulfato group is present, the water solubility is increased and in such case a greater amount of the dye will go into solution.

Widely varying amounts of dye can be used in the dyeing operation. The amount of dye used can be, for example, /3 to 3% (by Weight) of that of the textile material although lesser or greater amounts of dye can be employed.

This application is a continuation-in-part of my copending applications Serial No. 631,468 filed November 28, 1945, now U. S. Patent 2,516,302;

Serial No. 631,469 filed November 28, 1945, now U. S. Patent 2,516,303; Serial No. 109,056, filed August 6, 1949 and Serial No. 114,913 filed September 9, 1949. N difluoroalkylaminobenzene compounds are described and claimed in my copending application Serial No. 624,943 filed October 26, 1945, now U. S. Patent 2,516,107. N-trifiuoroalkylaminobenzene compounds are described and claimed in my copending application Serial No. 624,942 filed October 26, 1945, now U. S. Patent 2,516,106.

I claim:

1. The azo compounds having the general formula:

CHzOzS N=N N OzCHa X wherein R represents a member selected from the group consisting of a CH2CHF2 group, a -CH2CF'3 group, a CH2CF2CH3 group, a CH2CH2CHF2 group and a -CH2CH2CF3 group, R1 represents a member selected from the group consisting of a B-hydroxyethyl group, a li-hydroxypropyl group, a 'y-hydroxypropyl group and a p,' -dihydroxypropyl group, X represents a member selected from the group consisting of a hydrogen atom, a chlorine atom, a bromine atom, a methyl group and an ethyl group, Y represents a hydrogen atom and Z represents a member selected from the group consisting of a hydrogen atom, a chlorine atom and a bromine atom and wherein Y also represents a methoxy group when X is a chlorine atom or a bromine atom, and the sulfato form thereof.

2. The azo compound having the formula:

cHcCH z CHZCHZOH OzCHa 3. The azo compound having the formula:

SOzCHa CHzCHzOH 4. The azo compound having the formula:

SOzCHz CHzCFa CHZCH OH 5. The azo compound having the formula:

6. The azo compounds having the formula:

CHzCHF;

CHzCHgOH 21 hydrogen atom, a. chlorine atom, a, bromine atom, a. methyl group and an ethyl group and Z represents a member selected from the group consisting of a. hydrogen atom, a chlorine atom and a bromine atom.

7. The sulfato form of the azo compounds defined by claim 1.

JOSEPH B. DICKEY.

REFERENCES CITED Number 22 1 UNITED STATES PATENT Name Date Reddelien et a1 June 12,1928 Felix et a1 June 1, 1937 Dahlen et a1 Apr. 26, 1938 Felix et a1 Feb. 14, 1939 Dickey July 25, 1950 Dickey July 25, 1950 

1. THE AZO COMPOUNDS HAVING THE GENERAL FORMULA: 